Magnetic coating composition with four component epoxy binder



p 3,474,073 Ice Patented Oct. 21, 1969 are other shortcomings frequently encountered with most 3,474,073 magnetic Coatings. u MAGNETIC C(BATING COMPGSITKON WITH FOUR In accordance with this invention, a magnetic coating COMEPONENT EPOXY BINDER composition is provided which is particularly useful as Louis Higfishi, Monte Sereilo, Calif 355E110! t the magnetic coatings for the memory storage disks of Memo? Comoratiun, Santa Clam, e a the abovementioned type. The coating provides a mag- Pomfifin of California netic recording surface on the disk with sufficiently good No Drawing. Continuation-impart of application Ser. No.

mechanical properties that the coated disks can be used 23 123 93; 1967. This applicant, June 1968 substantially indefinitely without head crashing and with- Int. Cl. Cosg 51/02; G11], 5 /70 out loss of magnetic signals. Additionally, the coatings 5 CL 252 2,54 6 Cl i are resistant to the solvents commonly used in cleaning the disks, and the coatings may be applied to disks by a wide variety of techniques including spin coating, roll coating, knife coating, and spray coating.

ABSTRACT OF THE DISCLOSURE A tough, non-dusting magnetic coating with excellent A fluid, heat curable magnetic coating composition solvent resistance and good adhesion to aluminum is in which magnetic particles are dispersed in a four comprepared by curing a magnetic dispersion containing a ponent thermosetting epoxy binder. The coating also conbinder of a mixture of a high equivalent weight epoxy tains volatile solvents and a flow control agent which polymer, a low equivalent weight epoxy polymer, and 21 preferably includes epoxy groups which chemically bind mixture of an alkylated amine aldehyde condensation the flow control agent to the binder when the binder is product and a primary amine.

cured. The epoxy binder contains (1) a high equivalent The high equivalent weight epoxy polymer has an weight epoxy with a molecular weight of about 40() average of between one and three epoxy groups per mole- 4000 per epoxy group, (2) a low equivalent weight epoxy cule and a molecular weight per epoxy group of between with a molecular weight of about 130-1211 per epoxy 25 about 4004000. Preferably the high weight epoxy polygroup, (3) a large proportion of an amine aldehyde conmer is a condensation polymer of epichlorohydrin and densation product having secondary amine groups, and bisphenolAhaving the general formula 11 on, I OH; i i I i i on2orroHz-0 I OCH2CHCH2OC 0 01126110112 (4) a smaller proportion of a poly amine having primary Where It is an integer between about 2 to 10. The preamine gro 40 ferred condensation polymer of epichlorohydrin and bisphenol A which is employed in the practice of this in- This a cation is a continuationdl} art of m vention is a product sold by the Shell :Chemical Compending eigplication Ser. No. 619,017, file zt Feb. 27, 1967 ,Pany the trademark EPon 1001 Wind} has an epoxand now abandoned ide equivalent of 425550 and melting point of 6575 C. Other polymers which may be used in place of the Summary Of lfllentlon Epon 1001 are Shell Chemical Company Epon 1007, hav- Magnetic coating compositions have been made with a 5 an FP q nt W ight of 19002450 and meltwide variety of binder systems both thermoplastic and mg polflt of 5 f D W Chemical D.E.R. thermosetting, and many of these magnetic coatings have Clba Araldlie 6071, UIIIOH r d P astics ERR- very desirable properties for particular applications, How- 2011, General M1115 Gen P Y 525, Jones'Dabney P ever, substantially all of these magnetic coatings have Rel and Re1?hh1d EPOtuf 6301- A dit nally, the disadvantages from the standpoint of their magnetic propf P commerclany avallable P y s may be used erties, their physical ability to withstand abrasion, and 0f h Epon 10015 Shell p 9 n ral Mills their processing characteristics, that is the techniques EPOXY 9 w 664, clba Araldite 6084, which are required for their application to supporting Unlon Carblde Plastlcs ERR 2013, Epimembers Rez 530-C and Reichhold Epotuf 6304.

The requirements of a magnetic coating composition The low equivalent Weight ePOXY Polymer contains are particularly stringent where the composition is to be an average of between three and four epoxy groups P employed for making the magnetic recording layers for molecule and has a molecular Welght P P Y gfOuP 0f flying head memories such as the IBM 1311 Disk Stop between about 130-1211. The preferred low equivalent age drives. In memories of this type, a magnetic layer is Welght epoxy Polymer 1s an epoxylated Phenolic novolac provided on a rigid disk, usually made of aluminum, and sold by the DOW Chemlcal Company under the tradethe disk is rotated at speeds of about 1,500 r.p.m. while mark 438 and has the general formula a magnetic head is supported adjacent to the disk and O O 0 caused to fly aerodynamically over the disk surface. These 65 OCH E OCH O v CH 011 high rotational speeds of the dlsk, together with the high I 2 2 l 2 2 l 2 CH2 relative speeds of head and disk surface cause most magnetic coatings to shed magnetic oxide from the coating ultimately resulting in head crashing and damage to the l J magnetic heads and coatings. Lack of hardness, adhesion 11 to aluminum, impact resistance, toughness and resistance where n has an average value of 1.6. D.E.N. 438 has to solvents which are commonly used in cleaning the disks an average molecular weight of 571 and an average 3 equivalent weight of 159. In place of the D.E.N. 438 the following commercially available plastics may be used: Dow Chemical D.E.N. A85 and D.E.N. EK85 which are 85% solids solution in acetone and methylethylketone respectively, Ciba EPN 1138 and EPN 1139, and Union Carbide Plastics ERR-0100.

The amine aldehyde condensation product is a poly amine having a preponderance of secondary amine groups and preferably at least three amine groups per molecule. The preferred amine aldehyde condensation product is an alkylated melamine-formaldehyde conversion resin sold by the Monsanto Chemical Company under the trademark Resimene RF 5307 as a 90% solids solution in isopropanol. This resin has the following structural formula for its monomer.

H 1 70111013 i? N H I II E HooHlNo CNCHzOR where R may be an alkyl group of from one to four carbon atoms. While this is the structural formula for the monomer, the resin contains appreciable amounts of dimers and trimers of this structure. The molecular weight of the monomer is 272 and the equivalent weight is 91. In place of the RF 5307, the following commercially available resins may be used: American Cyanamid Cymel 350 and Monsanto Resimene RF 5306 and butylated urea-formaldehyde condensation polymers such as Monsanto UF-901, American Cyanamid Beetle 227-8, and Reichhold Beckamine P13 8-60.

The polyamine has at least one primary amine group per molecule, and the presence of this primary amine in the binder mixture has been found to be essential to the provision of satisfactory coatings. Absent the primary amine, the amine aldehyde condensation product undergoes homopolymerization at temperatures below the copolymerization temperature of the epoxy polymers and the amine aldehyde condensation product. The preferred poly amine with primary amine groups is N-aminoethylpiperazine which has the following general formula with a molecular weight of 130 and equivalent weight 43.3:

CHzCfig In place of the N-aminoethylpiperazine, the following polyamines may be used: N-(trimethoxysilylpropyl)ethylenediamine, diethylenetriamine and ethylenediamine.

When the epoxy binder is thermally cured, the amine groups in the amine aldehyde condensation product and in the polyamine react with the epoxy groups in the two epoxy polymers to provide a thermoset polymer matrix which is adherent to substrates such as aluminum and which forms an excellent binder for the magnetic particles. The amine and epoxy polymers are preferably provided in approximately stoichiometric quantities, but an excess of either can be used, that is the epoxy polymers are present in a sufficient amount that the combined number of epoxy groups in the polymers is between about 0.5 and 1.5 times the total number of hydrogen atoms on the primary and secondary amine groups in the polyamine and the condensation product.

The two epoxy polymers are preferably employed in sufficient amounts that they contribute approximately equal numbers of epoxy groups to the coating composition, and these amounts may be varied to some extent so that the ratio of the number of epoxy groups in the high equivalent weight polymer to the number of epoxy groups in the low equivalent weight polymer is within the range between about 3 to 1 and l to 3. Excessive amounts of the high equivalent weight polymer causes a tendency to dust in the cured epoxy coating, and excessive amounts of the low equivalent weight epoxy polymer results in embrittlement of the coating.

The polyamine with primary amine groups should be used in a sufiicient amount that the number of primary amine groups in the polyamine is between about 3 and 15 percent of the total number of epoxy groups in the two polymers. Where an insufficient quantity of primary amine is employed, homopolymerization of the amine aldehyde condensation product results, and where excessive amounts of the primary amine are employed the pot life of the coating composition is seriously reduced. Where the N-aminoethylpiperazine is employed as the polyamine. it is employed in an amount such that the equivalent ratio of N-aminoethylpiperazine to total epoxide in the polymers is between 0.1 and 0.4 and preferably about 0.2. The butylated melamine-formaldehyde condensation product is preferably used in an amount of 15 percent of the total weight of melamine and epoxy polymers.

Flow control agents are normally incorporated in highly pigmented coatings such as magnetic dispersions to serve a dual purpose of preventing the formation of pinholes in the cured coating and to promote adequate flow to smooth out surface defects such as orange peel and streaking. In accordance with this invention, a flow control agent is used which is preferably either one of the two following epoxy silane formulas: 3,4-epoxycyclohexylethyltrimethoxy silane having the general formula @cmcnpqoomh and glycidoxypropyltrimethoxysilane, having the general formula 61201101120cmomomsuoonm The former of these silanes is sold by the Union Carbide Company under the trademark A-186 Silane and the latter is sold by the Union Carbide Company under the trademark A-187 Silane.

Other flow control agents may be used, but their effectiveness is substantially poorer than the epoxy silanes mentioned above. Other flow control agents include General Electric SR82 silicone resin and Dow Corning DC84O which is a methylphenylpolysiloxane. The epoxy silanes provides most effective flow control prior to cure of the coating, and the epoxy groups on these silanes chemically bond the flow control agent to the binder so that the flow control agent does not adversely effect the properties of the cured coating.

The use of these silanes in the specific coatings mentioned below resulted in cured coatings with as-coated arithmetic average surface roughness of 8 to 14 microinches as measured on a profilometer. Ultimately such surfaces were easily polished to a surface roughness of approximately 2 microinches.

Magnetic coating compositions prepared in accordance with this invention and containing magnetically susceptible particles may be applied to flexible substrates such as Mylar or to rigid substrates such as aluminum or plastic plates employing such techniques as roll coating, knife coating, spin coating, and spray coating. Magnetic oxide particles are preferably incorporated into such coating compositions in amounts between about 60 and 120 parts by weight of magnetic oxide particles per parts of the binder with between about 100 and 400 parts of volatile solvents per 100 parts of the combined weight of binder and magnetic oxide particles. Various types of magnetically susceptible pigments may be employed, however, the magnetic pigment which was used in the example set forth below had the following magneitc properties when measured on a 60 cycle hysteresis loop tracer, using a symmetrical cyclic magnetic field of 1000 oersteds.

Magnetic property: Value Residual saturation (Br) Gauss 1750-2100 Maximum saturation (Bm) do 3300-3600 Coercive force (Hc) ..oersteds 275-300 Detailed description EXAMPLE I Component Proportions Solids Magnetic oxide 1. 45. 1 45. 1 60% Epon 1001 in Cellosolve 55. 2 33. 1 85% D.E.N. 438 in methylethylketone 14. 4 12. 2 90% Resirnene RF5307 in isopropanol 9. 8. 1 100% N-aminoethylpiperazine 1. 2 1. 2 60% SR-82 silicone resin in xylene.-- 0. 0. 3 80/10/10 Cellosolve/hexanol-l/Xylene.- 98. 0

Totals 223. 4 100. 0

A magnetic dispersion was prepared from the foregoing formulation in the following manner:

A mixture of 45.1 parts of magnetic pigment and 56.5 parts of solvent was mixed with a high speed mechanical stirrer and allowed to wet out by standing overnight. Subsequently, 36.3 parts of 60% Epon 1001 solution in Cellosolve were added to the pigment slurry and then milled until free of agglomerates. This mill base was then let down with a mixture containing 0.5 part of 60% SR 82 silicone resin solution, 14.4 parts of 85% D.E.N. 438 solution, 9.0 parts of 90% 'Resimene RF 5307, 18.9 parts of 60% Epon 1001 solution and 34.0 parts of 80/ 10 Cellosolve/hexanol-l/xylene solvent. Finally, 1.2 parts of N-aminoethylpiperazine are added together with 7.5 parts of 80/10/ 10 Cellosolve/hexanol-l/xylene solvent for adjustment of viscosity to approximately 360 cps. at C. as measured by a Brookfield viscometer using a #2 spindle at a speed of 20 rpm.

The coating was then applied to aluminum disks, prebaked for 15 minutes at 105 C. and cured for 4 hours at 185 C. Upon cooling the coating was polished to a roughness of approximately 2 to 3 microinches. Several complete disk storage packs each containing four parallel disks with eight storage surfaces and two outer-disks each containing one storage surface were assembled for testing.

The disks when tested on an IBM 1311 Disk Pack drive which was connected to a 1401 computer with 6 programs ran error free at high speed for over eight hours of testing without any evidence of wear, dusting or headcrashing. No measurable deterioration in magnetic performance was observed at the end of the testing period.

EXAMPLE IV Component Proportions Solids Magnetic oxide 45. 0 45. 0 60% Epon 1001 in Cellosolve 54. 6 32. 8 85% D.E.N. 438 in methylethylketone 14. 1 12. 0 90% Resimene RF 5307 in isopropanol 8.9 8. 0 100% N -aminoethylpiperazine 1. 1 1. 1 100% A-186 silane 1. 1 1. 1 30/70 toluene/methylcarbitol 98. 6

Totals 223. 4 100. 0

EXAMPLE V Component Proportions Solids Magnetic oxide 45. 0 45. 0 60% Epon 1001 in Cellosolve 54. 6 32. 3 85% D.E.N. 438 in methylethylketone 14. 1 12. 0 90% Resimene RF 5307 in isopropanol-.. 8. 9 8. 0 100% N-arninoethylpiperazlne 1. 1 1. 1 60% DC-840 silicone resin in toluene. 1. 8 1. 1 50/50 methylcarbitol/toluene 97. 9

Totals 223. 4 100. 0

EXAMPLE VI Component Proportions Solids Magnetic oxide 45.0 45. 0 60% Epon 1001 in toluene 54. 6 32. 8 85% D.E.N. 438 in methylethylketone. 14. 1 12. 0 90% Resirnene RF 5307 in isopropanol. 8. 9 8.0 100% N-aminoethylpiperazine 1. 1 1. 1 60% DC840 silicone resin in toluene. 1. 8 1. 1 50/50 methylcarbitol/toluene 07. 9

Totals 223. 4 100. 0

EXAMPLE VII Component Proportions Solids Magnetic oxide 45.0 45. 0 60% Epon 1001 in toluene.... 55. 0 33. 0 85% D.E.N. 438 in rnethylethylketone. 14. 1 12. 0 90% Resirnene RF 5307 in isopropanol. 8. 8 7. 9 100% N-aminoethylpiperazine 1. 1 1. 1 100% A-186 silane 1. 0 1. 0 20/80 diethylcarbitol/l-notropropane 60. 7

Totals 185. 7 100. 0

EXAMPLE VIII Component Magnetic oxide Totals .1

EXAMPLE IX Component Proportions Solids Magnetic oxide 34. 4 34. 4 60% Epon 1001 in solvent 1 42. 73 25. 638 85% D.E.N. 438 in MEK 5. 544 4. 712 90% Resimene 740 in isopropan 3. 750 3. 375 100% N-aminoethylpiperazine 0. 670 0. 670 Additional solvent 1 58. 536

1 Solvent is parts Cellosolve, 10 parts xylene and 10 parts hexanol.

EXAMPLE X C ornponent Proportions Solids Magnetic oxide 50. 0 50.0 40% Epon 1007 in Cellosolve 115. 27 96. 1 D.E.N. 438 in MEK 2. 24 1. 90% Resimene 740 in IPA- 1. 92 1. '73 N -aminoethylpiperazine 0. 27 0. 27 Solvent 80:10:10 116. 64

7 8 I claim: where R is an alkyl group containing about one to 1. A magnetic coating composition containing magfour carbon atoms, and; netically susceptible particles dispersed in a fluid thermo- (D) said polyamine is N-aminoethylpiperazine. setting binder where said binder comprises an intimate CHZCH2 admixture of:

(A) a high equivalent weight epoxy polymer contain- HN NhCZHSNH" ing an average of between 1 and 3 epoxy groups per CH2CH2 molecule and a molecular Weight P p y g p 3. The magnetic coating composition of claim Ti f t n a t 400 and 4000, characterized further by the inclusion of between about a W equivalent Weight p y P y containing 10 l and 5 weight percent, based on the weight of said binder. an a ag of between 3 and 4 P Y groups P of an epoxy-silane flow control agent selected from the molficule and a molecular Weight P P Y group class consisting of 3,4 epoxycyclohexylethyl trimethoxy of between a ut 130 and 1 silane and glycidoxypropyl trimethoxy silane. (C) an amine-aldehyde condensation product having 4. A fluid, heat curable magnetic coating composition more than two secondary amine groups per molecule, om ri ing; and (A) an epoxy binder comprising: (D) a polyamine having at least one primary amine (1) about 33 parts by weight of a condensation group per molecule, polymer of epichlorohydrin and bisphenol A (B) said epoxy polymers being provided in sufiicient having the general formula H CH3 CH3 i I I i CH2CHCHg0OO OCH CHCH2-OOCOOCEHCHCHZ (LH3 i (LE3 amounts that the ratio of the number of epoxy where .n is an integer from2to 10, groups in the high equivalent weight polymer to the (2) about 12 parts by weight of an epoxylated number of epoxy groups in the low equivalent weight phenolic novolac having the general formula polymer is within the range between 3 to 1 and l O O O to 3, I a (F) said polyamine being present in a sufiicient amount OCHNHCH that the number of primary amine groups in said CH; CH; polyamine is between about 3 and 15 percent of the total number of epoxy groups in said polymers, and (G) the polymers being present in sufficient amounts n that the combined number of epoxy groups in said Where the average Value of n is about polymers is between about 0.5 and 1.5 times the about 8 Parts y Weight of 311 alkylated melatotal number of hydrogen atoms on the primary and 40 mine-formaldehyde resin having tha 111 secondary amine groups in said polyamine and said formula condensative product. H 2. The magnetic coating composition of claim 1 in ECHZOH which:

(A) said high equivalent weight epoxy polymer is a F condensation polymer of epichlorohydrin and bis- HOCHZNC CNCHZOR phenol A having the general formula H CH3 1 CH2 0 J o I (L 0 umerical-0OTQoombnom-oO 0CH2611\CH2 CHa |11 C HQ whet? Is an mfeger m 2 to 10; Where R is an alkyl group containing about l to (B) said low equivalent weight epoxy polymer is an 4 carbon atoms and epoxylated phenolic novolac having the general (4) about 1 part by Weight of N amin0ethy1 formula piperazine,

0 0 (B) between about and 120 parts by weight of Came/Q3112 Como/EEK] OCHZ6H\OHZ 6O gzfggnetic oxide particles per 10l) parts of said binder CH2 (C) between about 100 and 400 parts, per 100 parts of the combined weight of said binder and particles. n of volatile solvents with said binder and particles uniformly dispersed therein.

5. The magnetic coating composition of claim 4 characterized further by the inclusion of about one part by H weight, per part by weight of said N-aminoethylpiperazi'ne. NCHQOH of an epoxy-silane flow control agent selected from the C class consisting of 3,4-epoxycyclohexylethyl tllHlGthOXY where the average value of n is about 1.6; (C) said condensation product is an alkylated melamineformaldehyde resin having the general formula N N silane and glycidoxypropyl trimethoxy silane. H H 6. A magnetic recording member comprising: HOCHzNC CNCHZOR (A) a substantially rigid disc formed of a non-magnetic material, and

N (B) a heat cured coating on said disc with said coating amount that the number of primary amine groups in said polyamine is between about 3 and 15 percent of the total number of epoxy groups in said polymers, and

(7) the polymers being present in sufficient amounts that the combined number of epoxy groups in said polymers is between about 0.5 and 1.5 times the total number of hydrogen atoms on the primary and secondary amine groups in said polyamine and said condensative product.

References Cited UNITED STATES PATENTS epoxy group of between about 400 and 4000,

(2) a low equivalent weight epoxy polymer containing an average of between 3 and 4 epoxy groups per molecule and a molecular weight per 10 epoxy group of between about 130 and 1211,

(3) an amine-aldehyde condensation product 'having more than two secondary amine groups per molecule, and

(4) a polyamine having at least one primary 15 3,148,082 9/1964 Di Ricco et al 117 132 amine Group per molecule 3,269,974 8/1966 Ch11ds 260-37 3,321,438 5/1967 BIOOkfiI et al 260 -47 (5 said epoxy polymers being provided in sufficlent amounts that the ratio of the number of TOBIAS E. LEVOW, Primary Examiner epoxy groups in the high equivalent weight polymer to the number of epoxy groups in the low 20 A DEMERS Asslstant Exammer equivalent weight polymer is within the range U S C1 XR between 3 to 1 and 1 to 3, (6) said polyamine being present in a sufiicient 117-161, 234, 235, 236, 237; 26 '37, 824, 830, 834 

